Exploring the Impact of Successive Redox Events in Thin Films of Metal–Organic Frameworks: An Absorptiometric Approach

Metal-organic frameworks (MOFs) featuring redox activity are highly appealing for electrocatalytic or charge accumulation applications. An important aspect in this field is the ability to address as many redox centers as possible in the material by an efficient diffusion of charges. Herein, we investigate for the first time the charge diffusion processes occurring upon two sequential one-electron reductions in an MOF thin film. Two pyrazolate-zinc(II)-based MOFs including highly electro-deficient perylene diimide (PDI) ligands were grown on conducting substrates, affording thin films with double n-type electrochromic properties as characterized by spectroelectrochemical analysis. In depth electrochemical and chronoabsorptiometric investigations were carried out to probe the charge diffusion in the MOF layers and highlighted significant differences in terms of diffusion kinetics and material stability between the first and second successive reduction of the redox-active PDI linkers. Our results show that MOFs based on multiredox centers are more sensitive to encumbrance-related issues than their monoredox analogues in the context of electrochemical applications, an observation that further underlines the fundamental aspect of careful pore dimensions toward efficient and fast ion diffusion.